JPH10302832A - Sodium-sulfur battery - Google Patents
Sodium-sulfur batteryInfo
- Publication number
- JPH10302832A JPH10302832A JP9108764A JP10876497A JPH10302832A JP H10302832 A JPH10302832 A JP H10302832A JP 9108764 A JP9108764 A JP 9108764A JP 10876497 A JP10876497 A JP 10876497A JP H10302832 A JPH10302832 A JP H10302832A
- Authority
- JP
- Japan
- Prior art keywords
- negative electrode
- sodium
- aluminum
- positive electrode
- sulfur battery
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Secondary Cells (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明はナトリウム−硫黄電
池に関するもので、さらに詳しく言えば、ナトリウムイ
オン伝導性の固体電解質管の開口部に接合されたα−ア
ルミナリングの一方の面または他方の面に負極蓋、正極
蓋を熱圧接合する接合方法の改良に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a sodium-sulfur battery, and more particularly, to one or other surface of an .alpha.-alumina ring joined to an opening of a solid electrolyte tube having sodium ion conductivity. And a method for hot-press bonding the negative electrode cover and the positive electrode cover to each other.
【０００２】[0002]
【従来の技術】ナトリウムイオン伝導性の固体電解質管
の内部に負極室を、外部に正極室を形成してなるナトリ
ウム−硫黄電池は、３５０℃という高温で作動させる完
全密閉構造の電池で、前記負極室は前記固体電解質管の
開口部に接合されたα−アルミナリングの一方の面に接
合された負極蓋によって密閉され、前記正極室は前記α
−アルミナリングの一方の面または他方の面に接合され
た正極蓋によって密閉されてなる。2. Description of the Related Art A sodium-sulfur battery in which a negative electrode chamber is formed inside a sodium ion conductive solid electrolyte tube and a positive electrode chamber is formed outside is a completely sealed battery operated at a high temperature of 350 ° C. The negative electrode chamber is sealed by a negative electrode lid joined to one surface of an α-alumina ring joined to the opening of the solid electrolyte tube, and the positive electrode chamber is filled with the α
-Sealed by a positive electrode lid joined to one or the other surface of the alumina ring.
【０００３】このようなナトリウム−硫黄電池としては
特開平６−３６７９６号公報に記載されたようなものが
知られており、その構造を図３および図４の要部断面図
によって説明する。[0003] As such a sodium-sulfur battery, one described in Japanese Patent Application Laid-Open No. 6-36796 is known, and its structure will be described with reference to cross-sectional views of main parts in FIGS.
【０００４】すなわち、図３のナトリウム−硫黄電池
は、固体電解質管１の上端にα−アルミナリング２がガ
ラスはんだ接合され、このα−アルミナリング２の上面
にアルミニウムまたはアルミニウム合金層１２を介して
負極蓋３が、下面にアルミニウムまたはアルミニウム合
金層１２を介して正極蓋４がそれぞれ熱圧接合され、前
記負極蓋３には負極端子５が溶接されるとともに、その
中央部を貫通して負極集電体としての負極パイプ６が溶
接され、この負極パイプ６の下方は内部に金属繊維７が
配された前記固体電解質管１内に挿入されてなり、約１
５０℃の保温下において前記負極パイプ６より固体電解
質管１内を排気した後、同温度で溶融させたナトリウム
８を真空充填し、充填後負極端子５の上端を封止して負
極室構成体とし、この負極室構成体を、円筒形の硫黄成
形体１０が挿入され正極集電端子１１が溶接された正極
集電体を兼ねる電槽９内に挿入してその上端を前記正極
蓋４と真空溶接してなるものである。That is, in the sodium-sulfur battery shown in FIG. 3, an α-alumina ring 2 is joined to the upper end of a solid electrolyte tube 1 by glass soldering, and an aluminum or aluminum alloy layer 12 is provided on the upper surface of the α-alumina ring 2. A negative electrode cover 3 is heat-pressure-bonded to the lower surface thereof through an aluminum or aluminum alloy layer 12. A negative electrode terminal 5 is welded to the negative electrode cover 3, and the negative electrode terminal 3 penetrates the center of the negative electrode cover 3. A negative electrode pipe 6 serving as an electric body is welded, and a lower portion of the negative electrode pipe 6 is inserted into the solid electrolyte tube 1 in which a metal fiber 7 is disposed.
After the inside of the solid electrolyte tube 1 is evacuated from the negative electrode pipe 6 while keeping the temperature at 50 ° C., the sodium 8 melted at the same temperature is vacuum-filled, and after filling, the upper end of the negative electrode terminal 5 is sealed to form a negative electrode chamber construct. The negative electrode chamber constituting body is inserted into a battery case 9 also serving as a positive electrode current collector in which a cylindrical sulfur molded body 10 is inserted and a positive electrode current collecting terminal 11 is welded, and the upper end thereof is formed with the positive electrode lid 4. It is made by vacuum welding.
【０００５】一方、図４のナトリウム−硫黄電池は、α
−アルミナリング２の上面に負極蓋３と正極蓋４とが熱
圧接合されてなる以外は図３のナトリウム−硫黄電池と
同一である。On the other hand, the sodium-sulfur battery shown in FIG.
3 is the same as the sodium-sulfur battery of FIG. 3 except that the negative electrode cover 3 and the positive electrode cover 4 are heat-pressure bonded to the upper surface of the alumina ring 2.
【０００６】上記したナトリウム−硫黄電池では、負極
蓋３、正極蓋４の材質は鉄またはステンレスであり、こ
の負極蓋３、正極蓋４とα−アルミナリング２との熱圧
接合はアルミニウムまたはアルミニウム合金層１２を介
して真空中または不活性気体雰囲気中で５５０〜６３０
℃の温度下、１０〜５０ＭＰａの圧力下で行われてい
る。In the above-mentioned sodium-sulfur battery, the material of the negative electrode cover 3 and the positive electrode cover 4 is iron or stainless steel, and the heat and pressure bonding between the negative electrode cover 3 and the positive electrode cover 4 and the α-alumina ring 2 is made of aluminum or aluminum. 550-630 in vacuum or in an inert gas atmosphere through alloy layer 12
It is performed under a temperature of 10C and a pressure of 10 to 50 MPa.
【０００７】[0007]
【発明が解決しようとする課題】上記した従来のナトリ
ウム−硫黄電池では、鉄またはステンレスからなる負極
蓋３、正極蓋４の熱膨張係数とα−アルミナリング２の
熱膨張係数との差によって熱圧接合後に接合部に残留応
力が生じ、それによって接合強度が低下するという問題
があった。In the above-mentioned conventional sodium-sulfur battery, the thermal expansion coefficient of the negative electrode cover 3 and the positive electrode cover 4 made of iron or stainless steel is different from the thermal expansion coefficient of the α-alumina ring 2. There has been a problem that a residual stress is generated in the joint after the pressure joining, thereby reducing the joining strength.
【０００８】また、負極蓋３とα−アルミナリング２お
よび正極蓋４とα−アルミナリング２との熱圧接合時
に、その間に介在させるアルミニウムまたはアルミニウ
ム合金層１２が負極蓋３および正極蓋４中に拡散するた
め、接合部にＡｌ5 Ｆｅ2 やＦｅ3 Ａｌなどの合金層が
生成し、この合金層の厚さが数十μｍ以上に達すると長
期間の使用とともに接合強度が低下するという問題があ
った。When the negative electrode lid 3 and the α-alumina ring 2 and the positive electrode lid 4 and the α-alumina ring 2 are joined by heat and pressure, the aluminum or aluminum alloy layer 12 interposed therebetween is formed between the negative electrode lid 3 and the positive electrode lid 4. Alloy layers such as Al 5 Fe 2 and Fe 3 Al are formed at the joints, and when the thickness of the alloy layers reaches several tens μm or more, the joint strength decreases with long-term use. was there.
【０００９】[0009]
【課題を解決するための手段】上記課題を解決するた
め、請求項１記載の発明は、固体電解質管の開口部にα
−アルミナリングが接合されてなり、前記α−アルミナ
リングの一方の面にアルミニウムまたはアルミニウム合
金層を介して負極蓋が接合され、この負極蓋によって密
閉される負極室と、前記α−アルミナリングの一方の面
または他方の面にアルミニウムまたはアルミニウム合金
層を介して正極蓋が接合され、この正極蓋によって密閉
される正極室とを備えてなるナトリウム−硫黄電池にお
いて、前記負極蓋、正極蓋の、少なくとも一方はクロマ
イズ加工された鉄または鉄−クロム合金からなり、前記
クロマイズ加工された負極蓋、正極蓋のアルミニウムま
たはアルミニウム合金層に接する表面に生成した炭化ク
ロム層の厚さを３〜２０μｍにしたことを特徴とするも
のである。In order to solve the above-mentioned problems, the invention according to the first aspect of the present invention relates to a method for manufacturing a solid electrolyte tube, comprising the steps of:
An alumina ring is joined, a negative electrode lid is joined to one surface of the α-alumina ring via an aluminum or aluminum alloy layer, and a negative electrode chamber sealed by the negative electrode lid; A positive electrode lid is joined to one surface or the other surface via an aluminum or aluminum alloy layer, and a positive electrode chamber closed by the positive electrode lid. At least one is made of chromized iron or iron-chromium alloy, and the thickness of the chromium carbide layer formed on the surface of the chromized negative electrode cover and the positive electrode cover in contact with the aluminum or aluminum alloy layer is 3 to 20 μm. It is characterized by the following.
【００１０】請求項１記載の発明によれば、炭化クロム
層の熱膨張係数はアルミニウムまたはアルミニウム合金
層や負極蓋または正極蓋の材質である鉄または鉄−クロ
ム合金の熱膨張係数より小であり、α−アルミナリング
の熱膨張係数より大であるので、熱圧接合後に生じる残
留応力を緩和することができる。また、炭化クロム層は
アルミニウムまたはアルミニウム合金や鉄を固溶した
り、これらと反応することがないため、アルミニウム層
の一部が負極蓋または正極蓋中に拡散して熱圧接合部に
Ａｌ5 Ｆｅ2 やＦｅ3 Ａｌなどの合金層が生成するのを
抑制することができる。また、生成した炭化クロム層の
厚さを３〜２０μｍにしたことにより、炭化クロム層が
厚くなりすぎてクラックを生じたり、剥離したりして熱
圧接合部の強度を低下させることなく、上記した効果が
得られる。According to the first aspect of the present invention, the coefficient of thermal expansion of the chromium carbide layer is smaller than the coefficient of thermal expansion of the aluminum or aluminum alloy layer or iron or iron-chromium alloy which is the material of the negative electrode cover or the positive electrode cover. , Α-alumina ring, it is possible to reduce the residual stress generated after the thermocompression bonding. In addition, since the chromium carbide layer does not dissolve or react with aluminum, an aluminum alloy, or iron, a part of the aluminum layer diffuses into the negative electrode cover or the positive electrode cover, and Al 5 Generation of an alloy layer such as Fe 2 or Fe 3 Al can be suppressed. In addition, by setting the thickness of the generated chromium carbide layer to 3 to 20 μm, the chromium carbide layer becomes too thick to cause cracking or peeling, thereby lowering the strength of the hot-pressure bonded portion. The effect obtained is as follows.
【００１１】また、請求項２記載の発明は、請求項１記
載の発明において、負極蓋、正極蓋の母材の鉄または鉄
−クロム合金の炭素含有率は０．１〜０．６％であるこ
とを特徴するものである。The invention according to claim 2 is characterized in that, in the invention according to claim 1, the carbon content of iron or iron-chromium alloy of the base material of the negative electrode cover and the positive electrode cover is 0.1 to 0.6%. It is characterized by having.
【００１２】請求項２記載の発明によれば、クロマイズ
加工によって生成する炭化クロム層にクラックが生じた
り、炭化クロム層が剥離して熱圧接合部の強度が低下す
ることはない。According to the second aspect of the present invention, no crack is generated in the chromium carbide layer generated by the chromizing process, and the chromium carbide layer does not peel off, and the strength of the hot-pressed joint does not decrease.
【００１３】また、請求項３記載の発明は、請求項１記
載の発明において、クロマイズ加工された負極蓋、正極
蓋のアルミニウムまたはアルミニウム合金層に接する表
面に生成する炭化クロム層は面粗度を３μｍ以下にする
ことを特徴とするものである。According to a third aspect of the present invention, in the first aspect of the invention, the chromium carbide layer formed on the surface of the chromized negative electrode cover and the positive electrode cover in contact with the aluminum or aluminum alloy layer has a surface roughness. The thickness is set to 3 μm or less.
【００１４】請求項３記載の発明によれば、α−アルミ
ナリングと負極蓋および正極蓋との熱圧接合部の強度を
向上させることができる。According to the third aspect of the present invention, it is possible to improve the strength of the hot-pressed joint between the α-alumina ring, the negative electrode cover and the positive electrode cover.
【００１５】（評価試験１）本発明のナトリウム−硫黄
電池の負極蓋および正極蓋の母材として用いられるステ
ンレスとして、炭素含有率がＡ：０．０３％、Ｂ：０．
１％、Ｃ：０．３％、Ｄ：０．４％、Ｅ：０．５％、
Ｆ：０．６％およびＧ：０．７％のものを準備し、重量
比で１０〜６０％のクロム粉末、０．５〜２．０％の塩
化アンモニウム粉末および残余のアルミナ粉末とともに
鉄箱内に封入し、約１１５０℃の水素気流中で数時間加
熱してクロマイズ加工を行った後、光学顕微鏡によって
炭化クロム層の厚さを測定したところ、表１のような結
果が得られた。(Evaluation Test 1) As stainless steel used as a base material for the negative electrode cover and the positive electrode cover of the sodium-sulfur battery of the present invention, the carbon content is A: 0.03%, B: 0.
1%, C: 0.3%, D: 0.4%, E: 0.5%,
Prepare an F: 0.6% and G: 0.7% iron box together with 10 to 60% by weight chromium powder, 0.5 to 2.0% ammonium chloride powder and the remaining alumina powder. After performing chromizing by heating in a hydrogen stream at about 1150 ° C. for several hours, the thickness of the chromium carbide layer was measured by an optical microscope. The results shown in Table 1 were obtained.
【００１６】表１から、炭素含有率が０．０３％のもの
では炭化クロム層の生成が認められず、炭素含有率が
０．１％になると炭化クロム層の生成が認められること
がわかった。From Table 1, it was found that the formation of a chromium carbide layer was not recognized when the carbon content was 0.03%, and the formation of a chromium carbide layer was recognized when the carbon content was 0.1%. .
【００１７】[0017]
【表１】 [Table 1]
【００１８】上記のようにクロマイズ加工したＡ〜Ｇ
を、それぞれ負極蓋と正極蓋としてα−アルミナリング
の上下面にアルミニウムまたはアルミニウム合金層を介
して真空中で温度を６００℃、圧力を５０ＭＰａとして
熱圧接合した。なお、この評価試験１では前記α−アル
ミナリングの内周面には固体電解質管の開口部を接合せ
ず、前記正極蓋には硫黄成形体を挿入しない電槽を溶接
した測定用サンプルを製作し、負極蓋に溶接した負極端
子の上端の開口部から液圧を導入して負極蓋とα−アル
ミナリングとの接合部に引張応力を印加することによっ
て熱圧接合部の強度を調査し、結果を表２に示す。な
お、熱圧接合部の強度は負極蓋とα−アルミナリングと
の接合部がリークしたときの液圧である。A to G which are chromized as described above
Were thermally and pressure-bonded in vacuum at a temperature of 600 ° C. and a pressure of 50 MPa via an aluminum or aluminum alloy layer on the upper and lower surfaces of an α-alumina ring as a negative electrode cover and a positive electrode cover, respectively. In this evaluation test 1, a sample for measurement was produced by welding a battery case in which an opening of a solid electrolyte tube was not joined to the inner peripheral surface of the α-alumina ring and a sulfur molded body was not inserted into the positive electrode lid. Then, the strength of the thermo-compression joint is investigated by introducing a liquid pressure from the opening at the upper end of the negative electrode terminal welded to the negative electrode lid and applying a tensile stress to the junction between the negative electrode lid and the α-alumina ring, Table 2 shows the results. The strength of the hot-pressed joint is the liquid pressure when the joint between the negative electrode lid and the α-alumina ring leaks.
【００１９】[0019]
【表２】 [Table 2]
【００２０】表２から、炭化クロム層の厚さが３〜２０
μｍであれば、熱圧接合部の強度を高くできることがわ
かる。From Table 2, it can be seen that the thickness of the chromium carbide layer is 3-20.
It can be seen that if it is μm, the strength of the hot-pressed joint can be increased.
【００２１】（評価試験２）評価試験１で使用した、炭
化クロム層の厚さが１０μｍ、１３μｍおよび２０μｍ
のものについて、炭化クロム層を、微粒の研磨剤を用い
たバフ加工による機械研磨によって面粗度が１，２，
３，４，５および６μｍになるように調整したものを準
備した。そして、これらを負極蓋と正極蓋としてα−ア
ルミナリングの上下面にアルミニウムまたはアルミニウ
ム合金層を介して評価試験１と同条件で熱圧接合し、同
様の測定用サンプルを製作した。そして、評価試験１と
同条件で負極蓋とα−アルミナリングとの接合部に引張
応力を印加することによって熱圧接合部の強度を調査
し、表３の結果を得た。なお、面粗度は光学顕微鏡によ
る表面の観察によって判定した。また、調整前の面粗度
は６μｍ程度であった。(Evaluation Test 2) The thickness of the chromium carbide layer used in Evaluation Test 1 was 10 μm, 13 μm, and 20 μm.
The chromium carbide layer was subjected to mechanical polishing by buffing using a fine abrasive to have a surface roughness of 1, 2,
Those adjusted to 3, 4, 5, and 6 μm were prepared. Then, these were heat and pressure bonded to the upper and lower surfaces of an α-alumina ring via an aluminum or aluminum alloy layer under the same conditions as in Evaluation Test 1 as a negative electrode cover and a positive electrode cover, thereby producing a similar measurement sample. Then, the tensile strength was applied to the joint between the negative electrode lid and the α-alumina ring under the same conditions as in Evaluation Test 1 to investigate the strength of the hot-pressed joint, and the results in Table 3 were obtained. The surface roughness was determined by observing the surface with an optical microscope. The surface roughness before the adjustment was about 6 μm.
【００２２】[0022]
【表３】 [Table 3]
【００２３】表３から、炭化クロム層の厚さを１０μ
ｍ，１３μｍとすれば面粗度が１〜６μｍのもので熱圧
接合部の強度を向上できることがわかるが、評価試験１
の結果を考慮し、炭化クロム層の厚さを３〜２０μｍと
すれば、面粗度は３μｍ以下の小さい方がよく、研磨の
手間などを考慮すれば、面粗度は１μｍ程度までとする
のが好ましい。According to Table 3, the thickness of the chromium carbide layer was 10 μm.
m and 13 μm, it can be seen that the surface roughness of 1 to 6 μm can improve the strength of the hot-pressed joint.
In consideration of the above results, if the thickness of the chromium carbide layer is 3 to 20 μm, the surface roughness is preferably as small as 3 μm or less, and if the labor of polishing is taken into consideration, the surface roughness is up to about 1 μm. Is preferred.
【００２４】（評価試験３）評価試験１で使用した炭化
クロム層の厚さが１３μｍのものについて、炭化クロム
層の面粗度が１μｍのもの、３μｍのもの、５μｍのも
のとを、５００℃の空気中に放置し、３０日間経過後の
熱圧接合部の強度を評価試験１と同条件で調査し、結果
を表４に示す。(Evaluation Test 3) With respect to the chromium carbide layer having a thickness of 13 μm used in the evaluation test 1, the chromium carbide layer having a surface roughness of 1 μm, 3 μm and 5 μm was measured at 500 ° C. , And the strength of the hot-pressed joint after 30 days was investigated under the same conditions as in Evaluation Test 1. The results are shown in Table 4.
【００２５】[0025]
【表４】 [Table 4]
【００２６】表４から、炭化クロム層の面粗度が１μｍ
のもの、３μｍのものでは、３０日間放置後でも熱圧接
合部の強度はほとんど変化しなかったのに対し、面粗度
が５μｍのものでは３０日間放置後では熱圧接合部の強
度は約７０％に低下した。このことから、炭化クロム層
の面粗度が３μｍ以下であれば、熱圧接合部の強度が確
保できることがわかる。According to Table 4, the surface roughness of the chromium carbide layer was 1 μm.
And 3 μm, the strength of the hot-pressed joint hardly changed even after being left for 30 days, while the strength of the hot-pressed joint was about 30 μm after leaving for 30 days. It has dropped to 70%. From this, it is understood that if the surface roughness of the chromium carbide layer is 3 μm or less, the strength of the hot-pressed joint can be ensured.
【００２７】[0027]
【発明の実施の形態】以下、本発明の実施の形態を図１
および図２に基づいて説明する。FIG. 1 is a block diagram showing an embodiment of the present invention.
A description will be given based on FIG.
【００２８】図１に示したナトリウム−硫黄電池の特徴
は、負極蓋３の、α−アルミナリング２上面のアルミニ
ウムまたはアルミニウム合金層１２と接する表面に厚さ
が１３μｍ、面粗度が１μｍの炭化クロム層１３を形成
したこと、正極蓋４の、α−アルミナリング２下面のア
ルミニウムまたはアルミニウム合金層１２と接する表面
に厚さが１３μｍ、面粗度が１μｍの炭化クロム層１３
を形成したことであり、図２に示したナトリウム−硫黄
電池の特徴は、負極蓋３の、α−アルミナリング２上面
のアルミニウムまたはアルミニウム合金層１２と接する
表面に厚さが１３μｍ、面粗度が１μｍの炭化クロム層
１３を形成したこと、正極蓋４の、α−アルミナリング
２下面のアルミニウムまたはアルミニウム合金層１２と
接する表面に厚みが１３μｍ、面粗度が１μｍの炭化ク
ロム層１３を形成したことである。The feature of the sodium-sulfur battery shown in FIG. 1 is that the surface of the negative electrode cover 3 in contact with the aluminum or aluminum alloy layer 12 on the upper surface of the α-alumina ring 2 has a thickness of 13 μm and a surface roughness of 1 μm. The chromium carbide layer 13 having a thickness of 13 μm and a surface roughness of 1 μm is formed on the surface of the positive electrode cover 4 which is in contact with the aluminum or aluminum alloy layer 12 on the lower surface of the α-alumina ring 2.
The feature of the sodium-sulfur battery shown in FIG. 2 is that the surface of the negative electrode cover 3 having a thickness of 13 μm on the surface of the upper surface of the α-alumina ring 2 which is in contact with the aluminum or aluminum alloy layer 12 has a surface roughness of 13 μm. Formed a chromium carbide layer 13 having a thickness of 1 μm, and formed a chromium carbide layer 13 having a thickness of 13 μm and a surface roughness of 1 μm on the surface of the positive electrode cover 4 in contact with the aluminum or aluminum alloy layer 12 on the lower surface of the α-alumina ring 2. It was done.
【００２９】そして、負極蓋３とα−アルミナリング２
および正極蓋４とα−アルミナリング２とは、真空中で
温度を６００℃、圧力を５０ＭＰａとして熱圧接合し、
前記負極蓋３に負極端子５を溶接し、固体電解質管１内
にナトリウム８を真空充填するとともに、前記正極蓋４
に硫黄成形体１０が挿入された電槽９を溶接して本発明
の実施の形態に係るナトリウム−硫黄電池とした。Then, the negative electrode cover 3 and the α-alumina ring 2
And the positive electrode cover 4 and the α-alumina ring 2 are thermocompression-bonded in a vacuum at a temperature of 600 ° C. and a pressure of 50 MPa,
A negative electrode terminal 5 is welded to the negative electrode cover 3, and sodium 8 is vacuum-filled in the solid electrolyte tube 1.
The battery case 9 in which the sulfur molded body 10 was inserted was welded to obtain a sodium-sulfur battery according to the embodiment of the present invention.
【００３０】図１に示した本発明のナトリウム−硫黄電
池と図３に示した従来のナトリウム−硫黄電池および図
２に示した本発明のナトリウム−硫黄電池と図４に示し
た従来のナトリウム−硫黄電池について、それぞれ評価
試験２，３と同条件で熱圧接合部の強度を調査し、結果
を表５に示す。The sodium-sulfur battery of the present invention shown in FIG. 1 and the conventional sodium-sulfur battery shown in FIG. 3 and the sodium-sulfur battery of the present invention shown in FIG. 2 and the conventional sodium-sulfur battery shown in FIG. With respect to the sulfur batteries, the strength of the thermo-compression bonding portion was examined under the same conditions as in Evaluation Tests 2 and 3, respectively, and the results are shown in Table 5.
【００３１】[0031]
【表５】 [Table 5]
【００３２】表５から、本発明の実施の形態に係るナト
リウム−硫黄電池は、前述した測定用サンプルを用いた
評価試験２，３の結果と同様の結果が得られることがわ
かり、負極蓋３とα−アルミナリング２との熱圧接合部
の強度および正極蓋４とα−アルミナリング２との熱圧
接合部の強度を高められることがわかった。From Table 5, it can be seen that the sodium-sulfur battery according to the embodiment of the present invention can obtain the same results as those of the evaluation tests 2 and 3 using the above-described measurement samples. It has been found that the strength of the hot-pressed joint between the α-alumina ring 2 and the positive-pressure cover 4 can be increased.
【００３３】なお、本発明によるクロマイズ加工は電池
の放電生成物である腐食性の多硫化ナトリウムから、鉄
や鉄−クロム合金を保護するためのもので、各図におけ
る１３は本発明の炭化クロム層を示し、熱圧接合する面
以外にも炭化クロム層が生成することを妨げるものでは
ない。The chromizing process according to the present invention is for protecting iron and iron-chromium alloy from corrosive sodium polysulfide which is a discharge product of the battery. A chromium carbide layer other than the surface to be thermally and pressure-bonded.
【００３４】[0034]
【発明の効果】上記したとおりであるから、本発明のナ
トリウム−硫黄電池は、熱圧接合部の接合方法を改良す
ることにより、その信頼性を向上させることができ、ナ
トリウム−硫黄電池を長寿命化することができる。As described above, the reliability of the sodium-sulfur battery of the present invention can be improved by improving the joining method of the hot-pressed joint, and the sodium-sulfur battery can be used for a long time. Life can be extended.
【図１】本発明のナトリウム−硫黄電池の要部断面図で
ある。FIG. 1 is a sectional view of a main part of a sodium-sulfur battery of the present invention.
【図２】本発明のナトリウム−硫黄電池の要部断面図で
ある。FIG. 2 is a sectional view of a main part of the sodium-sulfur battery of the present invention.
【図３】従来のナトリウム−硫黄電池の要部断面図であ
る。FIG. 3 is a sectional view of a main part of a conventional sodium-sulfur battery.
【図４】従来のナトリウム−硫黄電池の要部断面図であ
る。FIG. 4 is a sectional view of a main part of a conventional sodium-sulfur battery.
１ 固体電解質管 ２ α−アルミナリング ３ 負極蓋 ４ 正極蓋 １２ アルミニウムまたはアルミニウム合金層 １３ 炭化クロム層 Reference Signs List 1 solid electrolyte tube 2 α-alumina ring 3 negative electrode lid 4 positive electrode lid 12 aluminum or aluminum alloy layer 13 chromium carbide layer
Claims (3)
の開口部にα−アルミナリングが接合されてなり、前記
α−アルミナリングの一方の面にアルミニウムまたはア
ルミニウム合金層を介して負極蓋が接合され、この負極
蓋によって密閉される負極室と、前記α−アルミナリン
グの一方の面または他方の面にアルミニウムまたはアル
ミニウム合金層を介して正極蓋が接合され、この正極蓋
によって密閉される正極室とを備えてなるナトリウム−
硫黄電池において、前記負極蓋、正極蓋の、少なくとも
一方はクロマイズ加工された鉄または鉄−クロム合金か
らなり、前記クロマイズ加工された負極蓋、正極蓋のア
ルミニウムまたはアルミニウム合金層に接する表面に生
成した炭化クロム層の厚さを３〜２０μｍにしたことを
特徴とするナトリウム−硫黄電池。An α-alumina ring is joined to an opening of a sodium ion conductive solid electrolyte tube, and a negative electrode lid is joined to one surface of the α-alumina ring via an aluminum or aluminum alloy layer. A negative electrode chamber sealed by the negative electrode lid, a positive electrode lid joined to one surface or the other surface of the α-alumina ring via an aluminum or aluminum alloy layer, and a positive electrode chamber sealed by the positive electrode lid. Sodium comprising-
In the sulfur battery, at least one of the negative electrode cover and the positive electrode cover is made of chromized iron or an iron-chromium alloy, and is formed on a surface of the chromized negative electrode cover and the positive electrode cover in contact with the aluminum or aluminum alloy layer. A sodium-sulfur battery, wherein the thickness of the chromium carbide layer is 3 to 20 [mu] m.
おいて、負極蓋、正極蓋の母材の鉄または鉄−クロム合
金の炭素含有率は０．１〜０．６％であることを特徴と
するナトリウム−硫黄電池。2. The sodium-sulfur battery according to claim 1, wherein the base material of the negative electrode cover and the positive electrode cover has a carbon content of iron or iron-chromium alloy of 0.1 to 0.6%. Sodium-sulfur battery.
おいて、クロマイズ加工された負極蓋、正極蓋のアルミ
ニウムまたはアルミニウム合金層に接する表面に生成す
る炭化クロム層は面粗度を３μｍ以下にすることを特徴
とするナトリウム−硫黄電池。3. The sodium-sulfur battery according to claim 1, wherein the chromium carbide layer formed on the surface of the chromized negative electrode cover and positive electrode cover in contact with the aluminum or aluminum alloy layer has a surface roughness of 3 μm or less. A sodium-sulfur battery characterized by the following.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9108764A JPH10302832A (en) | 1997-04-25 | 1997-04-25 | Sodium-sulfur battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9108764A JPH10302832A (en) | 1997-04-25 | 1997-04-25 | Sodium-sulfur battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH10302832A true JPH10302832A (en) | 1998-11-13 |
Family
ID=14492906
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9108764A Pending JPH10302832A (en) | 1997-04-25 | 1997-04-25 | Sodium-sulfur battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH10302832A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101385741B1 (en) * | 2012-12-27 | 2014-04-21 | 재단법인 포항산업과학연구원 | Insert material for thermal compression bonding of sodium sulfur battery |
-
1997
- 1997-04-25 JP JP9108764A patent/JPH10302832A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101385741B1 (en) * | 2012-12-27 | 2014-04-21 | 재단법인 포항산업과학연구원 | Insert material for thermal compression bonding of sodium sulfur battery |
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